Flameproofing of fibrous materials



Patented Sept. 27, 1949 FLAMEPROOFING OF FIBBOUS MATERIALS Florence M. Ford and William P. Hall, Wilmington, Del., assignors to Joseph Bancroft & Sons 00., Wilmington, Dcl., a corporation of Delaware No Drawing. Application June 10, 1944, Serial No. 539,798

4 Claims. 1

This invention relates to the fiameproofing of cellulosic and protein materials and is particularly useful in the fiameproofing of textile fabrics especially those used for wearing apparel wherein a non-toxic, durable, relatively odorless finish is desired without unduly altering the hand" and feel of the original fabric. 7

It has long been known that the treatment of, for example, cellulose with phosphoric acid solutions in the cold results in formation of unstable addition compounds which are immediately decomposed when treated with water. If the cellulose is heated after treatment with a phosphoric acid solution, reactions take place resulting ultimately in the highly degraded form of cellulose called hydrocellulose. It is therefore impossible, to the best of our knowledge, to obtain durable fiameproof cellulosic materials by the direct reaction between phosphoric acid solutions and cellulose.

In our previous application Serial No. 514,822,

filed December 18, 1943, now abandoned.'of which the instant application is a continuation in part, we have described a process involving the use of ortho-phosphoric acid (and similar acids) and urea (or materials similar to urea), by which process a durable fiameproof finish is imparted with greatly reduced degradation and tendering of the cellulose and protein materials.

The present application is directed to an im-.

reaction products a volatile or decomposable a1- kaline agent (such as ammonium hydroxide) which will temporarily increase the pH of the mixture in order to stabilize the solution when the additional ingredients are added as described below. After the solution has been applied to the material this volatile alkaline agent is removed or altered during the curing operation, thus bringing about a pH condition which is favorable 2 tion is an agent (such-as formaldehyde) which. inter alia, has strong affinity for the nitrogen containing compounds and tends to combine with them under the condition of the process to form complexes which would not be formed in its absence and which perform functions to be hereinafter pointed out.

Some of these complexes, which contain most of the acid groups, create a condition of steric hin- 10 drance when the acid groups react on the material during the curing operation and thus increases the bufieringaction already exerted by the nitrogen containing compound by virtue of the basic nitrogen it contains.

In general the last mentioned additional agent added, having afiinity for the nitrogen compound, also has afiinity under the conditions of the process for the reactive groups of the material to be flameproofed and this acts as an additional buffer by competing with the acid for these reactive groups.

After the solution, containing the ingredien described above, has been applied, the material is 'dried and cured which, as stated, drives off the volatile or decomposable alkaline agent and produces water insoluble compounds between the ingredients of the solution, and between these insoluble compounds and the material to be flameproofed, and between the ingredients of the solution and the material, thus imparting to the material durable flameproof properties with a minimum loss in strength qualities.

In carrying out the invention the ortho-phosphoric acid (or similar acids) and the urea (or similar nitrogen containing compound), are mixed and heated to a high temperature, say from about 260 F. to about 400 F., 365 F. being satisfactory in most instances. the desired temperature is preferably done rapidly. As soon as the desired temperature is reached, heat is cut off and the mixture allowed to cool. During the heating, complex reactions take place between the phosphoric acid and the urea, and between the acid and the products formed by the alteration of the urea at high temperatures; carbon dioxide, ammonia, and also water, are liberated, andthe heated mixture, if allowed to cool sufiiciently, sets to a solid rocklike mass, soluble in water.

To the products of heating, preferably shortly before'solidifylng, water is added approximately in amount equal to the loss of total weight experienced in the heating. Ammonia or like alkaline material and formaldehyde or like material are then added separately in the older men- The heating to Quanta solutionwhidimaythenbefurtherdilutedto anyddredooneentration.

'lheunmmiaktbevolatilealhlineagent (I dispusim). The amount of such agent addedshouldbesuiilcienttoadjmtthepfito suchavaluethatobjectiouableformationofinsolubb compounds is avoided, especially when Themefenedpflisontheorderoffromabout Thesolutioninthlsstateissub- Thealkaline'mtshmlldbe thesolutionhas beenappliedtotbeiibersforthereasonthat dm-ingmehheatingthereshouldbeareturn conditions. Ammonhunhydroxide,

beingdeeanpossbleandvolatileiswellsuited" forthepurpose. l'heammoniaalsomakes it pollbletouseasmallerquantityofureathan wouldotherwiseberequired. 'Iheurea,aswill appeaninpartactsasabuflenreducingthe actiondthem'lcacid. Theu'seoftoo much thispurposeis,

Incasethenitrogmeontainingcunpoumdand theacideithu-prelseatedorlmheatedproduces a solution of satisfactory pH giving satisfactory stahllitywheuthealdehydeisaddedtheadditionofalkalinebasesuchasammonia maybe sgsgggg the agiieifi ingthesuboeqtmtheatingofthemateriahthe aldehydereaciswiththecelluloseto some extart, this Ringing about a further buffering action. a

'ihe standard solution made from the phosphm'lc acid, urea, ammonia and formaldehyde, anddilutedwlthwatertothedairedextentis nowapplied,forexample,toafabrlcinanyconmtionalwayasbypaddinmimmersiomotaating, spraying rinting and other-forms of coating or impsegnmdtherwithorwithoutpressure.

Withrespecttothedilutionofthestandard 'mlumniaiemeenueu. Itistobenoted tlmtthechmicalssbmildbesottenonandinto themata'ialinamotmtsufilcienttoproducethe desiredflameproofclnracteristics. Itispreferable to have the inlution suilicientlyooneentratedtopermitofobtainingsufllcientmaterialby oneapplieation. Otherwkeitmaybenecessary torunthematerialthroughihemangletwoor moretimeswithorwithoutinterveningdryings.

"ihiahowevenaddstotheexpense'andistobe avoldedwheneverponible,

lthahopossibletoaddtheingredientsseparutelytothematerial. Porenmpleatextile fabrh: may be impregnated with a mixture of ureaandphosphorleacidwhichmayormaynot This impregnation to be followed by one of formaldehyde and ammonium hydroxide or only formaldehyde and then dried. After curing and washing a durable fiameproof material is obtained. This method of procedure, however, is not as desirable.

After the fabric has been treated with the solution, it is dried and then cured. The fabric may be dried by passing it through a drying m atmosphere, say of about 300 F. Where-such temperature is employed, the'cloth remains in the dryer about 30 seconds but only comes to 300 F. for a few seconds. The drying temperature may be somewhat lower or higher, with a. corresponding change in the length of time in the drier, the essential object being to remove the excess water from the cloth.

The dried fabric is now cured in a curing oven or the like at temperatures desirably ranging from about 270 F. to about 345 F. for a period of time ranging from 23 minutes to about 2 minutes. At 250 F. the time required for curing may run as high as 2 hours which is undesirably long. At a temperature of 400 F. the time for curing may be only seconds. The temperature and the time should be such as will effect the I contribute toward the durable fiameproofiing 'lliefol-lnalddiydeused,asilrillappearand as'.

properties of the finish.

It is obvious that the individual steps in the process, namely, application of the solution, drying, curing, washing, and drying may be carried out as individual steps, or. combined into fewer steps, or if desired run as a continuous process.

- It is evident that reactions take place between the ingredients of the treating mixture even in the cold; When heated together to high temperatures the nitrogen containing compound and the acid react and form a number of complex compounds which in the case of urea and phosphoric acid are soluble in water (provided the materials are not heated to too high a temperature and too long; for example, at 430 F., an insoluble product is formed) When ammonia and formaldehyde are added, further reaction takes place, but the materials formed are still soluble in water in the case of urea and phosphoric acid.

Subsequent curing, in the main, primarily brings about further reactions (in addition to those already taken place during preparation of the solution) between the ingredients of the solution and between the ingredients and the cellulose.

08 These reactions are primarily as follows: first, a

combination between the phosphoric acid group and the cellulose; second, a further reaction takes place between the urea and the phosphoric acid group; third, reactions take place between the 7 urea, some of which may already be in combination with phosphoric acid, and the formaldehyde, resulting in the formation in many cases of large complex molecules; fourth, a reaction takes place between formaldehyde and the cellulose.

havebemheatedadescribedandthendried. 7s Allthesereactions take placesimultaneously during the curing, one reaction competing with the other. For example, in the case of the cellulose, the urea, and the phosphoric acid, a competition takes place between the cellulose and the urea for the phosphoric acid. In other words, the urea acts as a buffer for the reaction between the cellulose and the phosphoric acid. The buffering action of the urea is enhanced by the large size of the nitrogen containing compounds caused by the combination between the formaldehyde and urea. This increase in buffering action is due, first, to the neutralizing action caused by the presence of a large number of basic nitrogen groups close to the phosphoric acid, and, second, to the steric hindrance effect caused by the large size of the aldehyde-nitrogen-phosphorus complex. This steric hindrance prevents the easy access of the phosphoric acid to the cellulose.

In addition, a further buffering action takes place as already stated by the action of the formaldehyde upon the reactive groups of the cellulose. This concurrent reaction competes with the phosphoric acid for the reactive groups of the cellulose and therefore acts as a buffer.

In the case of protein fibers such as wool, the same reactions take place, but in this case the groups in the protein fibers are much more reactive than the groups of the cellulose. Thus, for example, at a certain-concentration of formaldehyde excellent results may be obtained on cellulose but the results on wool are less satisfactory due to the excessaction between the aldehyde and the wool. This is the reason why our previous patent application where aldehydes were not used is better adapted to protein fibers. On protein fibers it is therefore best to use smaller percentages of aldehyde. To illustrate, if in Example 1 hereof, 5 parts of formaldehyde instead of parts are used, satisfactory results are obtained.

Whether or not the foregoing theories are correct, the fact remains that analysis of the finished product shows that when the aldehyde is used, the ratio of nitrogen to phosphorus is much larger, which would tend to establish that additional nitrogen groups are held in combination by means of the aldehyde. Some of these nitrogen groups are not held as firmly as the phosphorus groups. Repeated severe hot water washes reduce the nitrogen content until a ratio of phosphorusnitrogen is reached which corresponds closely to that obtained when the aldehyde is not used. Thus, while the increased nitrogen content may not be regarded as permanently lasting, nevertheless there is a binding which serves the distinct purpose of maintaining high nitrogen content and thus increased buffering action during the curing. And the product obtained has considerably increased strength.

The presence of the aldehyde groups in the,

finished product tends to reduce the swelling in water since the aldehyde has combined primarily with the groups having a high affinity for water, and thus decreases the ability of thesegroups to absorb water. Fabrics flameproofed without aldehyde swell and subsequently stiffen, relatively very considerably on subjection to water, whereas when the aldehyde is present the swelling and subsequent stiffening is only slight.

We have found that although the urea, phosphoric acid, water, ammonium hydroxide, and formaldehyde may be mixed cold and applied to the material, it is very beneficial to heat together the acid and the urea as previously described. For example, if the same quantity of ingredients are used, we find that the preheated mix first,

produces a solution of higher pH; second, imparts a higher pH to the finished, flameproofed material; third, reduces the swelling in water of the finished product; fourth, shortens the time of curing for the same temperature; and, fifth,

lessens the stiifness of the finished product. The

latter is especially important when the process is applied to materials such as garment fabrics.

The following four examples illustrate varia-- tions obtainable with the same chemical ingredients in different proportions and using different methods of application. These examples illustrate but do not limit the invention.

Example 1 parts of urea and 50 parts ortho-phosphoric acid (75%) were mixed and heated rapidly to 375 F. The resulting mixture was cooled, 75 parts of water was added, followed by the addition of .7 parts of ammonium hydroxide (28%.), and 10 parts of formaldehyde (37%). In this and the following examples, all parts given are by weight.

The resulting solution was water clear and a cotton fabric (herringbone twill) was impregnated with the same b passing it through a regular textile impregna ing mangle, the operation consisting in dipping the cloth into the solution followed by a squeeze to remove excess solu-' tion. Then followed drying on the regular tenter frame, the temperature being approximately 300 F. The cloth was allowed to remain in the frame long enough to remove the water by evaporation.

One section of the cotton fabric was cured at a temperature of 345 F. for a period of 2 minutes and 10 seconds. This was followed by washing in hot water and drying.

Another part of the same cloth was cured at 300 F. for a period of 13 minutes, this again being followed by the wash in hot water and drying.

The two samples were found to be substantially equal in flameproof qualities and the respective finishes were of substantially equal durability.

Example 2 A solution prepared in the identical manner described in Example 1 was made and consisted of 100 parts of urea, 50 parts of ortho-phosphoric acid (75%), 7 parts of ammonium hydroxide (28%), 50 parts of formaldehyde (37 and 50 parts of water.

The solution was water-clear and cotton cloth (herringbone twill) was again impregnated as described in the previous example and the cloth dried on the tenter frame as described.

One part of the cloth was cured at 345 F. for a period of 3 minutes and 40 seconds, followed by the usual wash in hot water and drying.

Another part .of the cloth was cured at 300 F. for a period of 22 minutes, this again being followed by washing in hot water and drying.

The two samples were substantially equally flameproofed and the durability of the finish was likewise substantially the same.

The essential difference between the solutions of Examples 1 and 2 is that in Example 2, 50 parts of formaldehyde were used instead of 10 parts as in Example 1. The increase in the quantity of formaldehyde increases the time required for curing.

It is also to be noted that with increase in the is reduced, and vice versa.

Imple 3 A solution was preparedas before, but consisted of 100 parts of urea, 50 parts of orthophosphoric acid (75%), 7 parts ammonium hydroxide (28%), 2'! parts of formaldehyde (37%) and 55 parts water.

The water-clear solution was applied to cotton fabric and the fabric dried in a tenter as described in the other examples.

The fabric was then cured at 250 1''. for a period of 2 hours, followed by the usual washing and drying procedure. The resulting fabric was found to be fiameproof and the flameprooilng qualities and the durability of the finish were quite satisfactory.

This example again shows that with decrease in the curing temperature a longer period for the cure is required. I

Example 4 The formula and method of procedure in this example was identical with that described in the previous example, but in this case the cotton cloth was cured at a temperature of 400 F. for a period of 30 seconds, fpllowed by the usual washin: and ying P The finish was both satisfactory and durable.

In all of the examples above given, the original "hand" and feel of the fabric was substantially retained, there was no obiectionable stiii'ness, there was little degradation or tendering, and the finished fabric had good tensile strength, tear strength, and little tendency to swell in water.

While the fabric will flame on application of a torch, on removal the flame goes out immediately and there is no afterglow. The finish is fast to dry cleaning, hot and cold water leaching, and to repeated laundry treatments with detergents such as Igepon T (a substituted amide of oleic aOid-C1'1HJ3CONMBCH:CH2SO:NE). It will and alkaline detergents without objectionable even withstand several mild washings with soap lossoffinish.

The ratio of urea to ortho-phosphoric acid is not critical, although it is to be noted that the urea should not be greater than approximately 10 mols to one mo} of phosphoric acid. This seems to be about the practical upper limit. It is also to be observed that with increase in urea content, there is an increase in the time required for curing. The general range of urea content is from 1 to 10 mols to one mcl ofphosphoric and the preferred range, giving the optimum results. is from 1.75 mols to 5 mols of urea to 1 mol of phosphoric acid.

\ by various substitution products of these constituents, it will be seenthat'theposible variations are great in number. However, the general observations herein made will serve as a guide in I any particular case.

In all the previous examples, use has been made of ortho-phosphoric acid (H3PO4) but other acids of phosphorus, such as, for example, ortho-phosphorus acid, meta-phosphoric acid, and pyrophosphoric may be used. Also substituted phosphoric acids have been tried and found satisfactory, such as, for example, monochlorphosphoric acid and phmphamic acid. Oxides of phosphorus which in the presence of water will form the acids may also be used; for example, good results have been obtained using phosphorus pentoxide.

.For example, a solution of 300 parts of urea, 100 parts phosphorus pentoxide, P205, 200 parts water, 100 parts ammonium hydroxide (28%) and 50 par-ts formaldehyde (37%) gave good results.

In place of the phosphoric acid we may use other strong acids such as, for example, sulphamic acid, in which case we have found, for example, that a solution consisting of 200 parts urea, 100 parts sulphamic acid, 100 parts water,

The amount of ammonium hydroxide is not critical in the sense that more ammonia may be added than is needed to secure the desired pH of the solution, any excess being driven off in the subsequent drying and curing operations. It

cause excessive dilution and to cause such a high pH as to interfere with stability of the solution. We have usually found it advantageotm to add fromJ/4 mol to 1 mol of ammonia (NHJ) to every mol of ortho-phosphoric acid used.

It will be seen that the percentages of aldehyde added may be varied between wide limits. If the aldehyde is kept very close to the lower limit, care must be exercised in curing as less buffering action takes place as described in the proposed mechanism. If excesively high content ofaldehyde is added. too much buffering action takes should not be used in amounts so'large as to 15 parts ammonium hydroxide (28%) and 50 parts formaldehyde (37%) gives good results.

We have also found that we may use concentrated sulphuric acid as well as phosphori and sulphamic acid. With a solution consisting, for example, of 180 parts urea, 60 parts sulphuric acid conc., 50 parts water, 15 parts ammonium hydroxide (28%) and 50 parts formaldehyde (37%), we have secured good results.

We have also used-mixed acids. For example, a solution consisting of 200 parts urea, 50 parts of ortho-phosphoric acid 50 parts of cone. sulfuric acid, parts of water, 15 parts ammonium' hydroxide (28%) and 50 parts formaldehyde (37%), gave good results.

The acid (or combination of acids) should be strong acids like those specifically mentioned, for they must be active enough to react, under the conditions of the process, with the cellulose and nitrogen containing compound and should contribute in the imparting of theflameprooflng properties. They should be substantially nonvolatile under the heat conditions of the process. Thus hydrochloric acid is unusable. They should not contain objectionable quantities of ingredients which would tend to increase the flammability, and therefore one. cannot use acids They should not react with the cellulose to pro- 70 duce explosive or flammable compounds. Thus nitric acid is unsuitable. A small amount of nitric acid could be used impartial substitution 'for the phosphoric acid forfiexample.

In general\we prefer to the strong inorplace and long curing is necessary. In fact lithe 7| ganic acids of the above characteristics as they have the necessary activity to combine with the material to be flameproofed'and with the other ingredients of the solution; and due to the absence of carbon in these acids they substantially contribute to the flameproofing qualities of the finished product.

The salts of such strong acids with volatile bases such as, for example, ammonium phosphate, and acid salts of the metallic elements may also be used providing the remaining acid properties of the acid are suflicient to perform the desired functions, and provided the metallic elements do not interfere excessively with the solubility of the ingredients of the mixture. Thus any metals precipitating the ingredients upon dilution are undesirable.

We may also use resins instead of formaldehyde. With a solution consisting, for example, of 75 parts urea, 50 parts phosphoric acid (75%), 53 parts water, 7 parts ammonium hydroxide (28%) and 160 parts of Aerotex Cream #450, a urea formaldehyde resin (40%), marketed by Calco Chemical Company, we have obtained good results. Other usable resins are water soluble phenol-formaldehyde resins and ketonealdehyde resins. For example- 200 parts urea, 100 parts ortho-phophoric acid (75%), parts ammonium hydroxide, 50 parts of water, and 100 parts of a ketone-aldehyde resin. The latter was prepared by refluxing together for 2 hours 250 parts of acetone, 535 parts of formaldehyde (37%), and 6.5 parts of sodium carbonate.

The above fiameproofing solution was applied as previously described and good fiameproofing results were obtained.

Another example of the use of resins is as follows: 100 parts of urea, 50 parts of orthophosphoric acid (75%), 25 parts water, 8 parts ammonium hydroxide, and 60 g. of a phenolformaldehyde resin. The last material was prepared by heating together 38 parts of phenol, 49 parts formaldehyde (37%), .4 part sodium carbonate, and 1 part ammonium hydroxide (28%). The flameproofing solution above was applied to cotton fabric in the usual manner, and the resulting product was firm but had good durable fiameproofing properties.

We may also use aldehydes other than formaldehyde. For example, a solution consisting of 200 parts urea, 100 parts phosphoric acid (75%), 114 parts water, '15 parts ammonium hydroxide (28%) and 50 parts of glyoxal (30%), gives good results. 1

As further illustrative, we may use a halogenated aldehyde instead of formaldehyde. A solution consisting of 200 parts urea, 100 parts phosphoric acid, (75%), 114 parts water, 15 parts ammonium hydroxide (28%) and 75 parts chloral hydrate, gives good results.

We have also employed a mixture of aldehydes. For example, a solution consisting of 200 parts urea, 100 parts ortho-phosphoric acid (75%), 100 parts water, 15 parts ammonium hydroxide (28%), 25 parts formaldehyde (37%), and 25 parts glyoxal (30%) gave good results.

Other aldehydes may be used such as, for example, a'cetaldehyde, acrolein and aldol. The aldehyde should be of low molecular weight (a carbon chain of from 1 to 4), reactive with the nitrogen containing compound and desirably also with the cellulose under the conditions of process as previously described. The length of the carbon chain should not be so great as to contribute measurably to the flammability of the finished 10v product and it becomes evident that in general the less the carbon content, the better the results obtained. Since an aldehyde of fairly strong activity is required, the low molecular weight aldehydes with very reactive aldehyde groups and short carbon chain such as those specifically mentioned should preferably be employed. These give the proper balance between nitrogen. phosphorus, and carbon present,so that satisfactory flameproofing properties are obtained.

We may use nitrogen compounds other than urea. Thus, for examp1e,-a solution containing 100 parts dicyandiamide, 200 parts phosphoric acid (75%), 100 parts water, 15 parts ammonium hydroxide (28%) and 25 parts formaldehyde (37%), gave good results.

As a further illustration, we may use biuret instead of urea. A solution consisting of 200 parts biuret, 100 parts phosphoric acid (75%) 150 parts water, 25 parts ammonium hydroxide (28%), 25 parts formaldehyde (37%), gives good results.

We may use amino guanidine carbonate (9. salt) instead of urea. A solution consisting, for example, of 100 parts aminoguanidine carbonate. parts phosphoric acid parts water, 25. parts ammonium hydroxide (26%) and 25 partsformaldehyde (37%), gave good results.

We have also used mixed nitrogen-containing compounds. For example, a solution consisting of parts urea, 100 parts aminoguanidine carbonate, 100 parts phosphoric acid (75%), 100

parts water, 15 parts ammonium hydroxide (28%) 50 parts formaldehyde (37%), gave good results.

We have used other salts. Urea sulphate and guanidine sulphate; and urea phosphate and guanidine and amino guanidine phosphates;

may be used instead of the urea and give good resu1ts.-

In general the nitrogen containing compound should contain nitrogen groups capable of reacting with the acid and the aldehyde of the reacting mixture to the desiredvextent. It should not contain large carbon chains which would contribute excessively to the flammability of the finished product, and should preferably contain a large percentage of nitrogen.

We prefer to use relatively weak nitrogen-containing bases, such as urea, for the reason that the process is easier to control. If relatively much stronger nitrogen bases be used, greater care in proportioning must be employed for the reason that such strong bases have correspondingly greater aflinity for the phosphorous groups than has the cellulose. Because of this, care must be exercised lest too much protective action is obtained which would result in loss of permanency, or too little, which would result in excessive tendering.

For example, the following flameproofing solution when applied to cotton fabrics gave flameproofing of unsatisfactory durability,*20 parts of guanidine carbonate, 40 parts ortho-phosphoric acid (78%), 20 parts water, 8 parts ammonium hydroxide (28%) and 10 parts formaldehyde The following formula caused excessive tendering when attempts were made to obtain satisfactory durable flameproofing properties on cotton fabrics. 30 parts guanidine carbonate, parts ortho-phosphoric acid (75%), 20 parts water, 8 parts ammonium hydroxide (28%) and 10 parts formaldehyde (37%).

The following formula gave satisfactory flameproofing when applied to cotton fabrics: 30 parts diamine and 50 parts formaldehyde (37%), gave good results We have also used a mixture of volatile bases instead of ammonium hydroxide. For example, a solution consisting of 200 parts urea, 100 parts phosphoric acid (75%) parts water, 7.5 parts ammonium hydroxide, 7.5 parts ethylene diamine and 50 parts formaldehyde (37%) gave good results.

In substitution of ammonium hydroxide, we may use any basic substance which will participate in the reaction as described, that is, make the solution stable prior to application, and will decompose or volatilize or both under the conditions of the process, to recreate the acid condicoatings on fabrics previously fianmmofed by theprocessheredescribed.

Inthecaseofgarmentfaln-mwehavemade use extensively of such additional mechanical andchemicalpmcessestoobtaindesiredresults. For example, softening agents in small quantities, so as nottointerferewiththe flameproofing properties, have been added to imtions which will bring about the necessary reactions. We may mention such products as trimethylamine, diethylamine, and triethylamine by way Of example. In general, the principles hold as previously outlined for other ingredients of the solutions in that the alkaline agent must be substantially soluble in the reaction mixture and not contain carbon chains which are large enough to contribute excessively to the flammability 0f the finished product.

We have heretofore indicated that the phosphoric acid and urea should be preheated before the addition of water, ammonia and aldehyde. This preheating may as already mentioned be omitted and the phosphoric acid and urea may be mixed in the cold. This, however, involves some sacrifice in the properties and does not represent the optimum results obtainable.

While we have mentioned a number of different acids, nitrogen compounds, volatile bases, and aldehydes, we prefer to use ortho-phosphoric acid, urea, ammonium hydroxide, and formaldehyde. The solution which we prefer to use consists substantially of 200 parts urea, 100 parts ortho-phosphoric acid (75%), 100 parts water, 15 parts ammonium hydroxide (28%) and 50 parts formaldehyde (37%).

We have used formulas as above described on rayon, rayon-wool, rayon-Aralac textile fabrics, as well as on cotton, with good results. (Aralac is a casein product.) On cotton goods we have obtained especially good finishes on herringbone twill, plain weave fabrics, sateen, ducks and similar fabrics. Satisfactory results can be obtained on animal fibers insofar as durability is concerned, but not as good as is the case in the process of the aforesaid application.

We have also obtained good results on paper, wood pulp and plain wood. Usually pressure in application is to be resorted to.

The flameproofing process here described may be used in conjunction with conventional chemical and mechanical treatment processes, either before or after the application of the flameproofing treatment, provided such processes do not interfere excessively with the fiameprooflng results obtained.

In the case of general textiles such additional processes may be used, as, for example, other flameproofing processes, softening treatments, water-proofin printing, dyeing or coating treatments. For example, excellent results have been obtained by coating nitrocellulose and vinylite prove the hand and strength of the fabric. Softening materials which are durable to subsequent washing treatments are especially useful, for example, the commercial products Zelan" (stearamidomethylpyridinium chloride) and No- Rane" (stearoyloxymethylpyridinium chloride) have been used as have other cation acting materials. Softening agents which are not durable may be used as well, such as lecithin, acetamide, sulfonated fatty matter, etc., but the results obtained with these products are not as desirable.

Variations are obtained by the condition of the material; for example, certain types of weaves are especially adapted while others are less so. Thus a herringbone twill gives excellent results while a hard twist, tightly woven twill is less adapted.

Where odor and toxicity and slow decomposition are of no consequence, other substances than those specifically herein mentioned may be employed providing they answer to the general requirements hereinbefore set forth.

Attention is called to the fact that certain portions of the subject matter disclosed herein are also disclosed and are claimed in our copending application Serial No. 596,592, filed May 29, 1945.

We claim:

1. In the art of producing a complex of acid and nitrogen with cellulose fibrous materials to impart durable flame and mildew resistance thereto, the method which consists in impregnating the fibrous material with an aqueous solution of (1) at least one substantially water soluble inorganic acid compound selected from the class consisting of acids of phosphorus and sulfur which are free of metal and of organic groups and of constituents yielding active oxygen or halogen nitrogen and has an atomic ratio of carbon to nitrogen not substantially more than the ratio of carbon to nitrogen in biuret, (3) a water solublue volatile alkaline compoimd in an amount sufficient to give to the solution a pH of from 6 to 8, and (4) an aldehyde compound chosen from the so class consisting of formaldehyde, hexamethylene tetramine, acetaldehyde, and glyoxal, the amount of said nitrogen containing organic compoimid in the solution having a ratio to the acid in the solution of from l mol to 10 mols to 1 mol of acid on the basis of orthophosphoric acid and the amount the equivalent of that applied by a single application, followed by a squeeze in a textile mangle to remove excess solution, with a solution containing the equivalent of from 10.8% to42% of orthophosphoric acid by weight and with the nitrogen 76 containing organic compound and the aldehyde Q present in relation to the acid in amounts within the ratios just above specified; drying the material, and heating the dried material to a temperature ranging from 400 F. to 250 F. for a time ranging from 30 seconds to 2 hours.

2. The process of claim 1 in which the temperature ranges from 345 F. to 290 F. and the time ranges from 2 to 40 minutes.

3. The process of claim 1 in which the ratio of organic nitrogen containing compound is from 1.75 mols to 5 mols to 1 mol of acid on the basis of orthophosphoric acid.

4. The process of claim 1 in which the acid is orthophosphoric, the nitrogen containing compound is urea, the alkaline agent is ammonium hydroxide, and the aldehyde is formaldehyde in the following proportions by weight:

Parts Orthophosphoric (75%) 100 Urea 200 Ammonium hydroxide (28%) 15 Formaldehyde (37%) 50 Water 100 FLORENCE M. FORD. WIILIAM P. HAIL.

REFERENCES CITED The following references are of record in the flle of this patent:

UNITED STATES PATENTS Number Name Date 1,436,231 Blenio Nov. 21, 1922 1,734,516 Foulds et a1. Nov. 5, 1929 2,049,217 Meunler July 28, 1931; 2,088,227 Battye et a1 July 27, 1937. 2,089,697 Groeb Aug. 10, 1937 2,098,082 Bowen et a1. Nov. 2, 1937 2,212,152 Cupery Aug. 20, 1940 2,233,475 Dreyfus Mar. 4, 1941 2,243,765 Morton May 27, 1941 2,267,277 Houk et a1. Dec. 23, 1941 2,274,363 Foulds et a1 Feb. 24, 1942 2,332,047 Bock et a1 Oct. 19, 1943 FOREIGN PATENTS Number Country Date 334,408 Great Britain Sept. 4, 1930 446,379 Great Britain Apr. 29, 1936 476,043 Great Britain Nov. 29, 1937 509,408 Great Britain July 11, 1939 510,199 Great Britain July 28, 1939 547,846 Great Britain Sept. 15, 1942 OTHER REFERENCES Ser. No. 233,292,- Schubert et al. (A. P. C.) pub. May 4, 1943.

Kleek, Fire Retardant Synthetic-Resin Paints, Amer. Chem. 800., News Ed., 19, 626-628 Certificate of Correction Patent No. 2,482,756 September 27, 1949 FLORENCE M. FORD ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 7, lines 42 and 43, strike out and alkaline detergents without objec tional even withstand several mild washings with soap and insert instead even withstand several mild washings with soap and alkaline detergents without objectionable; column 12, lines 56 and 57, for solublue read soluble; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 14th day of February, A. D. 1950.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

